Conjugated diene butyl

ABSTRACT

Dehydrohalogenation of halogenated butyl to produce a butyl rubber having conjugated double bonds in the linear backbone. The composition is disclosed as having the predominant structure:   WHERE N+1 REPRESENT THE NUMBER OF ISOOLEFIN UNITS INCORPORATED IN THE BUTYL RUBBER POLYMER BACKBONE, AND M REPRESENTS THE NUMBER OF CONJUGATED DIOLEFIN UNITS PRESENT, SUBSTANTIALLY AS ISOLATED UNITS. The composition is prepared by contacting a solution of halogenated butyl rubber with: (1) a soluble metal carboxylate, where the metal is selected from the metals of Groups Ib, IIb, IVa and VIII of the Periodic Table; (2) a soluble carboxylic acid; and (3) an oxide or hydroxide of a metal selected from the metals of Groups Ia or IIa of the Periodic Table.

Unite States Patent 1 1 Baldwin et al.

[451 June 11, 1974 1 1 CONJUGATED DIENE BUTYL [75] Inventors: Francis P. Baldwin, Summit, N..l.;

Alberto Malatesta, Brussels, Belgium [73] Assignee: Esso Research and Engineering Company, Linden, NJ. I

[22] Filed: Feb. 23, 1972 [21] Appl. No.: 228,727

[52] US. Cl. 260/79.5 C, 260/795 A, 260/795 B, 260/853 R, 260/853 C, 260/853 H [51] Int. Cl. C08d 3/10, C08d 5/02 [58] Field of Search..... 260/853 H, 85.3 R, 85.3 C, 260/795 [56] References Cited UNlTED STATES PATENTS 3,261,789 7/1966 Berger et a1. 260/5 3,646,166 2/1972 Canter et a1. 260/879 OTHER PUBLICATIONS Encyclopedia of Polymer Science and Technology, Vol. 2, pp. 777782, lnterscience, New York (1965).

Primary Examiner.loseph L. Schofer Assistant Examiner-A. Holler [57] ABSTRACT Dehydrohalogenation of halogenated butyl to produce a butyl rubber having conjugated double bonds in the linear backbone. The composition is disclosed as having the predominant structure:

13 Claims, No Drawings CONJUGATED DIENE BUTYL BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to conjugated diene butyl rubber containing conjugated unsaturation in the linear backbone, and a process of preparing same.

2. Description of the Prior Art The expression butyl rubber is used in the rubber industry to describe copolymers made from a polymerization reaction mixture having therein from 70 to 99.5% by weight of an isoolefin which has about 4 to 7 carbon atoms, e.g., isobutylene, and about 30 to 0.5% by weight of a conjugated multiolefin having from about 4 to 14 carbon atoms, e.g., isoprene. The resulting copolymers contain 85 to 99.5% by weight of combined isoolefin and about 0.5 to 15% of combined multiolefin. The preparation of butyl rubber is described in on. on:

CH =0 CH1=i3 -CH=CH2 isobutylene isoprene which combine in the presence of Friedel-Crafts catalysts to form:

where n+1 represent the number of isoolefin units incorporated in the butyl rubber, while m represents the number of initial diolefin units present, substantially as isolated units. The conjugated diolefm, isoprene, loses one olefinic linkage upon its essentially random incorporation into the polymer backbone.

Thus, butyl rubber, as presently produced, contains only a small percentage of unsaturation, in the form of the single double bond associated with the isoprene residue which is incorporated more or less randomly throughout the polymer chain.

Halogenated butyl rubber has been developed in recent years and has contributed significantly to the elastomer business. A method'of preparing halogenated butyl rubber is described in U.S.'Pat. No. 3,099,644, which is incorporated herein by reference. Both chlorinated and brominated butyl rubber are well known in the art. The formula for halogenated butyl rubber is typified by:

CH woa= on-onl onrii l- T in t (is.

where n, l and m have the same values as for butyl rubber, described above, though this structure is but one of several which can be formed, depending on the conditions of hztlogenation, the halogenating agent used, etc.

SUMMARY OF THE INVENTION It has now been discovered that dehydrohalogenation of halogenated butyl rubber produces a butyl rubber containing conjugated unsaturation in the linear polymer backbone. The general formula may be represented by:

where n, m and 1 have the values previously described, though other structures may be present, for example the structure:

DESCRIPTION OF THE PREFERRED EMBODIMENTS The preferred method of preparing the compositions of the present invention is to dehydrohalogenate a halogenated butyl rubber.

One of the preferred methods of accomplishing this is taught in copending application Ser. No., 228,728, filed on the same day as this application, by one of the present inventors, Francis P. Baldwin, which application is incorporated herein by reference.

Halogenated butyl rubber is commercially available and may be prepared by halogenating butyl rubber in a solution containing 1 to 60% by weight butyl rubber in a substantially inert C -C hydrocarbon solvent such as pentane, hexane, heptane, etc. and contacting this butyl rubber cement with a halogen gas for a period of about 2-25 minutes. There is then formed the halogenated butyl rubber and a hydrogen halide, the copolymer containing up to one or somewhat more, especially in the case of bromine, halogen atom per double'bond initially present in the copolymer. This invention is not intended to be limited in any way by the manner in which butyl rubber is halogenated or dehydrohalogenated and both chlorinated and brominated butyl rubber are suitable for use in this invention.

Illustrative of halogenated butyl rubber is Enjay Butyl HT 10-68 (a chlorinated butyl rubber which before halogenation analyzes 1.8 mole unsaturation and a viscosity-average molecular weight of about 450,000).

However, for the purposes of this invention, it is preferred that the butyl rubber starting material have incorporated therein from about 0.5 to 6% of combined diolefin, more preferably 0.5 to 3%, e.g. about 2%.

Conventional high molecular weight butyl rubber generally has a number average molecular weight of about 25,000 to about 500,000, preferably about 80,000 to about 250,000, especially about 100,000 to about 200,000, and a Wijs Iodine No. of about 0.5 to 50, preferably 1 to 15. More recent low molecular weight polymers are prepared to have number average molecular weights of from 5,000 to 30,000 and unsaturation, expressed as mole of 2-10.

Dehydrohalogenation is a known chemical reaction and reagents commonly used are listed, for example, on p. 1308 of Reagents for Organic Synthesis by Louis F. and Mary Fieser (John Wiley and Sons, Inc., New York, 1967). Among these are, for examples tbutylamine, N,N-dimethylformamide, calcium carbonate, potassium t-butoxide, sodium iodide in 1,2- dimethoxyethane, etc.

These methods and reagents have been employed with low molecular weight materials where homogeneous contacting of the material to be dehydrohalogenated with the dehydrohalogenating reagent is effected at high concentration, where compound and reagent solubilization can be effected by the use of polar solvents, e.g., dimethylsulfoxide, ethanol, diethyl ether, etc.

In high polymers where the halogen is present in the polymer only in small percentage, where the polymer is not soluble in polar solvents and where the concentration of the halogen containing polymer is limited by the high viscosity of polymer solutions in solvents, these methods of dehydrohalogenation are not suitable for producing the compositions of the present invention. Moreover, even in the case where the dehydrohalogenating reagent is hydrocarbon soluble, undesirable side reactions occur, which prevents formation of the products of this invention.

Forexample, dehydrohalogenation by tertiary amines can be considered conventional. The side reaction here is the formation of quaternary salts as in reaction 1 1) R-X N(R') RN(R) X where x halogen.

These salts when embedded in a medium of low dielectric constant (i.e., the polymer itself) lead to associated ionic complexes. In a high polymer this manifests itself in pseudo crosslinking leading to enormous increases in viscosity and gelation.

In summary then the most effective conventional reagents are insoluble in the systems of concern, and the soluble conventional reagents give undesirable side reactions.

A particularly advantageous method of preparing these polymers comprises heating a solution of the halogenated polymer in the presence of a soluble metal Carboxylate. Suitable metals are the polyvalent metals of Groups lb, llb, lVa and VII], of the Periodic Table, having a relatively high first ionization potential and whose halides are soluble in the hydrocarbon reaction medium at the reaction temperature. Typical of these are zinc, iron, mercury, nickel, copper, tin and cadmium carboxylates.

Especially useful are the soluble carboxylic acid salts of zinc (e.g., zinc salts of naphthenic acids). While useful in preparing the compositions of the present invention, potential toxicity problems which could be encountered in practicing the present invention might limit the use of certain metals, such as cadmium and mercury salts, for example.

Zinc carboxylate is the most preferred catalyst in the present invention. However, in dehydrohalogenating the halogenated butyl rubber, according to the present invention, zinc chloride is thought to be a by-product in the reaction. Zinc chloride, being an effective Frie del-Crafts type catalyst, may lead to molecular weight degradation or crosslinking of the halogenated polymers, depending on the structure of the polymer.

This difficulty is overcome, in the present invention, by having present in the reaction zone a metal oxide, hydroxide or carboxylate whose halogen salt is insoluble in the reaction medium.

For example, although not wishing to be bound thereby, it is thought that the invention proceeds by the following series of reactions:

i. Dehydrohalogenation by Zinc Carboxylate ii. Generation of Alkali or Alkaline Earth Carboxylate iii. Regeneration of Zinc Carboxylate and Elimination of Zinc Halide O Zu(Cl)z+Ca O-- -R 2 CaClgJ. Zn O--ii7-R 1 (soluble) (insoluble) Thus, by this series of reactions the zinc carboxylate, effective in dehydrohalogenation, perhaps by a concerted 6-membered ring mechanism route as depicted below:

can be regenerated, the net overall reaction in terms of transformation of materials being '7 i "an. Zn (0-( i-R); CH=( J-CHCICH For the purpose of this invention, reaction 7 must be repressed.

The relative participation of reactions 2 (or 5) and 7 can be adjusted by the solvent medium used, the temperature at which the reaction is run and other factors known to alter the competition between elimination and substitution reactions. The exact nature of the allylic halide present in the polymer will also influence the relative extents of the two reactions under a given set of conditions. Not all of the factors governing the ratio of the reactions effected can be set forth, but we can and do illustrate that the balance can be effected in some of the examples to be cited.

It has been found that the mole percent of conjugated diene unsaturation, in the products of this invention, run from about 0.5 to about 2.5. The mole percent of allylic ester is generally from about 0.1 to 0.25.

The conjugated diene-containing butyl rubber of this invention may be cured by a variety of methods, e.g., sulfur, sulfur-containing curing agents, polyfunctional dienophiles, and the like. Typical polyfunctional dienophiles are m-phenylene-bis-maleimide; ethylene glycol dimethacrylate; trimethylol propane trimethacrylate. Monofunctional dienophiles suitable for further modification of the polymer are cis-Z-butene diol; maleic anhydride; vinyl trichlorosilane; ally] alcohol; acrylic acid; crotonaldehyde; and the like. These are merely well known examples. There are many more polyfunctional dienophiles, well known in the art, that will cure the present compositions.

in addition, the known sulfur and sulfur-containing curing agents may be used to cure the present compositions.

The conjugated diene-containing compositions may also be covulcanized with other general purpose rubbers. Most suitable are the high unsaturation rubbers, such as natural rubber, SBR (a butadienestyrene rubber known formerly as GR-S) and the like. This is demonstrated in Example 8, hereinbelow. The amount of high unsaturation rubber that can be blended with the conjugated diene rubber of this invention is from about 10 to 90 weight percent.

The product of this invention will be more completely understood in reference to the following examples.

stirrer and reflux condenser on reactor and jacket, was charged with 50 grams of a chlorinated butyl rubber (Chlorobutyl HT 1068, manufactured by Enjay Chemical Company), 4 g. zinc naphthenate, 0.5 g. naphthenic acid, and 3 g. powdered lime (CaO). The zinc naphthenate, naphthenic acid and CaO were added after the rubber was dissolved. The reactor was then blanketed with nitrogen.

The vapor jacket, also charged with xylene, was then brought to reflux leading to a reactor temperature of about 138C. After 0.5, 1, 2 and 4 hours of heating, ml. samples were withdrawn from the reactor, placed in centrifuge tubes, diluted with approximately 30 ml. of hexane and centrifuged.

The clear fluid in the tubes was then slowly poured into rapidly agitated acetone to precipitate the polymer. The precipitate was then stored for 12 hours under 200 ml. acetone containing 0.2 g. of an antioxidant. The polymer was dried in a vacuum oven at about 50C. for 16 hours. I

Samples were submitted for chlorine analysis, the results of which are in Table I.

lowed to cool to ambient temperature after 4 hours of heating at 138C, was removed from the reactor and diluted with about 600 ml. hexane, the solids settled by gravity and the polymer contained in the clear supernatant fluid precipitated in acetone. The precipitate (designated Sample F) was treated in the same manner as the withdrawn samples in Table I.

After drying, the Sample F was compounded as follows:

Polymer Sample F parts M-phenylenebis-maleimide 4.5

A sample of this material was placed in a mold in a curing press for 60 minutes at 100C. On removal of the crosslinked vulcanizate, a sample was immersed in cyclohexane. At equilibrium the sample exhibited a swelling ratio (wt. of sample wt. of solvent/wt. of sample) of 3.62, indicating a highly crosslinked network.

Drying and reweighing of the swollen sample indicated insolubilization of greater than 96% of the polymer.

EXAMPLE 2 A 100 gallon, jacketed, glass-lined, stirred Pfaudler reactor was charged with:

1. 55 gallons of xylene 2. 53 pounds of diced Enjay Butyl HT 1068 3. 2 pounds of diced Butyl HT 1068 into which had been milled 275 grams of magnesium oxide grams of naphthenic acid analyzing 220 g./mole COOH 5. 860 grams of zinc naphthenate 6. 25 grams of Antioxidant 2246 The reactor was then heated to 132-134C. under nitrogen and held at this temperature for 4 hours. When the reactor had cooled, the polymer was precipitated from solution by the addition of 55 gallons of 99% isopropanol.

The supernatant fluid was then siphoned off and the precipitated polymer redissolved in 55 gallons of hexane and the polymer reprecipitated with isopropanol.

Again the supernatant fluid was siphoned off and the polymer redissolved in 450 pounds of hexane. To this solution were added 37.5 g. Antioxidant 2246 and the solution was then washed with 25-30 gallons of cold water. After, settling, the water was drawn off, 250 grams of finely powdered calcium stearate added and the cement drummed.

The polymer was then collected by boiling off the hexane in a steam/water bath, complete drying being effected by milling on a hot (-300F.) open rubber mill.

The analytical data obtained are as follows:

Feed Polymer Reaction Product Dimer Solution Viscosity Ratio 0805/0747 0806/0746 ((1.5/1)* lodine Number 7.1 12.2

Indicates solution concentrations. mg polymer/ml. isohutylcne dimer.

showing that the chlorine had been effectively removed, the iodine number increased and no molecular weight breakdown occurred.

Infrared and ultraviolet analyses, respectively, indicated the product contained:

mole '71 allylic ester 0034 mole 7r conjugated diene 1.37

A sample of this polymer when mixed with 4.50 grams of m-phenylene-bis-maleimide per 100 grams of polymer and heated in a mold for 2 hours at 275F. displayed a swelling ratio in cyclohexane (as defined in Example 1) of 4.17.

EXAMPLE 3 The reactor as described in Example 2 was charged with:

1. 55 gallons of xylene 2. 53 pounds of diced Enjay Butyl HT 1068.

3. 2 pounds of HT 1068 into which had been milled 400 grams of calcium hydroxide 4. 100 grams of naphthenic acid 5. 860 grams of zinc naphthenate 6. 12.5 grams of Antioxidant 2246 The reaction was conducted as before (4 hrs. at -134C.) and the polymer precipitated twice as before. However, the final solution was washed with -25 gallons of water containing 1 pound of glacial acetic acid and -3 gallons of 99% isopropanol. This dissolved all unreacted calcium hydroxide and caused rapid settling of the water layer.

The polymer was collected as before by solvent flashing and hot milling.

Analytical data on this run are as follows:

Feed Polymer Reaction Product Dimer Solution Viscosity Ratio (0.5/1) 0803/0746 0809/0749 lodine Number 7.36 11.8

Spectral examination indicated the reaction product to contain 0.119 mole allylic ester and 1.25 mole conjugated diene. Curing and swelling as in Example 2 gave a swell ratio of 3.80.

EXAMPLE 4 1n the procedure much as that used in Example 3, an error was made and only 60 grams of calcium hydroxide was added to the reactor. After reaction, the xylene solution was very thin indicating drastic reduction in the molecular weight of the polymer. This example then reveals the effect of insufficient group lla metal hydroxide to forestall accumulation of zinc chloride.

EXAMPLE 5 To a vapor jacketed 1 liter glass reactor equipped with stirring paddle were added:

1. 200 ml xylene 2. 50 grams of a low molecular weight chlorinated butyl 3. 1.5 grams of naphthenic acid 4. 4 grams of zinc naphthenate 5. 3 grams of calcium hydroxide After the polymer had dissolved, the jacket (containing xylene) was brought to reflux and reflux maintained for 4 hours. When the reactor had cooled, the solution was diluted with 200 ml. hexane and washed with 175 ml. water containing 10 m1. glacial acetic acid and ml. 99% isopropanol.

The wash water was drawn off in a separatory funnel, the solution evaporated on a steam bath by bubbling nitrogen through the hot solution until the total volume was about 225 ml. This solution was then poured into acetone, mulled around by hand and the supernatant fluid poured off. The polymer was then stored under fresh acetone for a few days and finally dried in a vacuum oven at 50-55C. for -22 hrs.

Analytical data are as follows:

Feed Polymer Reaction Product Dimer Solution Viscosity Ratio (2/1) 0.790/0.749 0793/0746 When 5 grams of this polymer were mixed by hand with 0.35 grams of 94% rn-phenylene-bis-maleimide, gelation was noticeable after 8 hours standing at room temperature and extensive crosslinking had occurred after a few days storage. After several weeks the vulcanizate displayed a swelling ratio in cyclohexane of 6.00 and 88.6% of the polymer had been insolubilized.

The compositions of this invention may be cured with TABLE I11 conventional curing systems. However, it had been discovered that the conventional accelerators, normally Run Number 6.1 6.2 6.3 used with high unsaturated rubber such as Natural rub- CDB 100 ber, SBR, and the hke, cause the present compositlons 5 Buty] I to be cured at essentially the same rate as with the so- SBR 1500 100 called ultra accelerators. 3% Black 2 2 Thus, in the following example, there is demon- Sulfur 1.6 1.6 1.6 strated the curability of the conjugated diene contain- Sanwcure l1 ing butyl rubber of this invention. T i| E| ti l Stress at 300% Elongation EXAMPLE 5 Cured '/290F. 2000-790 no cure no cure A masterbatch of conjugated diene containing butyl rubber referred to hereinafter as CDB, was prepared in mic") dumbbell a conventional manner, with a variety of accelerators, t5 shown in Table 11, below. The CDB was prepared in the All the mgredlents are Parts by 100 parts by welght same manner as in Example 1, above, and analyzed a of the rubbermole conjugated unsaturation of -1.19; and had a EXAMPLE 7 Wijs lodine No. of 10.4. The masterbatch contained (in parts by weight): 20 A pgrtlclllar avamage of the Present CDB t1ons 1s the1r ability to cure at h1gh temperatures with- CD3 out reversion. Curing rubber at high temperatures, e.g. SRF Black 50.0 c no 50 340 F. and higher, uslng convent1onal sulfurgttitttrlt. Acid g3 accelerator packages, frequently leads to the phenom- 13 111 ena of reversion, wherein suitable crosslink densities TABLE 11 CDB ACCELERATOR TESTS Acccleratoflphr) Swelling Ratio Run NO. Cure. Min. at 290F. 20 40 80 160 5.1 Ethyl Tuads 1.0) 6.99 3.77 2.98 2.94 5.2 Tellurac (1.0) 3.98 3.23 2.84 2.90 5.3 Santocure (1.0) 3.74 3.23 2.94 2.93 5.4 Santocure (2.0) 3.80 3.25 3.00 2.96 5.5 Captax (1.0) 7.19 5.56 3.64 3.36 5.6 Butyl Zimate (1.0) 6.61 4.43 3.20 3.18

'Swelling ratio described in Example 1. "'Px-441 is di(tert. buty1)p cresol.

The low swll ratio values shown in Table 11 indicate can neither be attained or maintained on continued relative high crosslink density. Most interesting is the heating at these temperatures. By contrast, curing the fact that the so-called ultra accelerators, e.g. Run CDB polymers of this invention with polyfunctional Numbers 5.1, 5.2 and 5.6, cause curing at about the dienophiles is effectively conducted at these higher same rate as the accelerators normally used with high temperatures. The resulting network has no tendency unsaturated rubber, i.e., Run Number 5.3, 5.4 and 5.5. to degrade on continued heating.

EXAMPLE 6 In order to illustrate this, a CDB, prepared in essentially the same manner as the CDB of Example 1, was

Runs were made to obtain a comparison of CDB Curcured with two polyfunctional dienophiles. The condiing time with the curing time for other rubber comtions and swell ratio are given in Table IV below. The pounds. Used in these runs was a butyl rubber and a CDB analyzed 0.04% chlorine, had a conjugated diene commercial SBR rubber. The rubber was compounded content of 1.39 mole and an lodine No. of 12.0 as follows, and the compounds cured for 20 minutes at (compared to an initial lodine No. of 6.1 in the chlori- 290F. nated butyl, Enjay HT 1068).

TABLE IV Run NO. 7.1 7.2 7.3 7.4 7.5

CDB 100.0 100.0 100.0 100 0 100.0 SR 207" 2.1 4 2 SR 350" 2.1 4.2

Cured 30'/320F. #100 14.41 17.8) 13.4( 14.1) 8.4(8.2) 7.3( 30'/340F. Slight gel 9.4(9.6) 9.2(74) 7.0(5.1) 6.5(5.2) 3()'/360F. 34.0(40.0 6.7(4.8) 6.7(4.8) 5713.4) 5.6(4.2) 30'/38()F. 21.21 15.6) 6.3(4.2) 6.2(3.6) 5.4(29) 5.5(39) "'Ethylene glycol dimethylacrylatc "'Trimcthyl propane trimethucrylate ""Solvcnt cyclohexanc NOTE:

The parts of ingredients are on a phr basis.

The low swell ratios indicate a high crosslink density.

Blends of CDB with other elastomers may be covulcanized to produce rubber compounds having interesting properties. It was found in this case that better physical properties were obtained by compounding the CD8 and other elastomer separate, followed by blending. This is opposed to a method where the rubber is blended on a mill. followed by addition of the cure package. This is illustrated in Table V, below, where Runs 8.1 and 8.2 are the two masterbatch preparations with the individual rubbers, CDB, and SBR-1500, respectively. Runs 838.5 are blends of these masterbatch preparations. Run 8.6 was prepared by blending the two rubbers, followed by addition, on the mill, of the black, oil, and cure package.

ASTM Dumbbell specimens were used to determine tensile, elongation, and stress at 300% elongation. Swelling ratio was determined as described in Example 1, with toluene used as the solvent.

The CDB was prepared in the same manner as in Example l, the sample having a mole conjugated diene unsaturation of -l.02.

wherein n+1 represent the number of isobutylene units incorporated in the copolymer backbone, and m represents the number of conjugated diene containing isoprene units present, substantially as randomly inserted units.

4. The composition of matter of claim 2, wherein there is combined in the copolymer from about 0.5 to

about 3.0 percent by weight isoprene, substantially all TABLE v CDB/SBR COVULCANTZATION Run No. 8.1 8.2 8.3 8.4 8.5 8.6

CDB 100.0 25.0 50.0 75.0 75.0 SBR-l500 100.0 75.0 50.0 25.0 25.0 Tensile-Elong. Stress at 300% E Swell Ratio Curcd 20'/290F. 1800-790 125-890 790-865 1190-735 1075-640 325-730 NOTE: All runs were compounded with the following package of materials; amounts are on a phr basis: Philblack 0 50.0;

Flexon 5110 10.0; ZnO 5.0; Stcaric Acid 1.5; Sulfur 1.75; Santocure A 1.0.

What is claimed is:

l. A composition of matter consisting essentially of a copolymer consisting of from 85 to 99.5% by weight of an isoolefin having from 4 to 7 carbon atoms, combined with 15 to 0.5% by weight of a conjugated diolefin having from 4 to 14 carbon atoms, containing in the linear backbone conjugated diene unsaturation, the copolymer having a number average molecular weight of from about 5,000 to 500,000.

2. A composition of matter consisting essentially of a copolymer consisting of from 85 to 99.5% by weight of isobutylene and from 15 to 0.5% by weight of isoprene, a major portion of the isoprene units combined therein having conjugated diene unsaturation, the copolymer having a number average molecular weight of from about 5,000 to 500,000.

3. The composition of matter of claim 2, having the general formula:

8. The cured composition of matter of claim 7, wherein said polyfunctional dienophile is m-phenylenebis-maleimide.

9. The cured composition of matter of claim 7, wherein said polyfunctional dienophile is ethylene glycol dimethacrylate.

10. The cured composition of matter of claim 7, wherein said polyfunctional dienophile is trimethylol propane trimethacrylate.

11. The composition of matter of claim 2, covulcanized with from 10 to weight percent of a high unsaturation rubber.

12. The composition of matter of claim 11, wherein the high unsaturation rubber is natural rubber.

13. The composition of matter of claim 11, wherein the high unsaturation rubber is SBR. 

2. A composition of matter consisting essentially of a copolymer consisting of from 85 to 99.5% by weight of isobutylene and from 15 to 0.5% by weight of isoprene, a major portion of the isoprene units combined therein having conjugated diene unsaturation, the copolymer having a number average molecular weight of from about 5,000 to 500,000.
 3. The composition of matter of claim 2, having the general formula:
 4. The composition of matter of claim 2, wherein there is combined in the copolymer from about 0.5 to about 3.0 percent by weight isoprene, substantially all of said isoprene units having conjugated diene unsaturation.
 5. The composition of matter of claim 1 cured with sulfur or a sulfur containing curing agent.
 6. The composition of matter of claim 2 cured with sulFur or a sulfur containing curing agent, or a combination of said sulfur and sulfur containing curing agent.
 7. The composition of matter of claim 2 cured with a polyfunctional dienophile.
 8. The cured composition of matter of claim 7, wherein said polyfunctional dienophile is m-phenylene-bis-maleimide.
 9. The cured composition of matter of claim 7, wherein said polyfunctional dienophile is ethylene glycol dimethacrylate.
 10. The cured composition of matter of claim 7, wherein said polyfunctional dienophile is trimethylol propane trimethacrylate.
 11. The composition of matter of claim 2, covulcanized with from 10 to 90 weight percent of a high unsaturation rubber.
 12. The composition of matter of claim 11, wherein the high unsaturation rubber is natural rubber.
 13. The composition of matter of claim 11, wherein the high unsaturation rubber is SBR. 